Cr Isotope Response to Ocean Anoxic Event 2

Abstract:

The element Cr offers a redox sensitive isotopic proxy with potential for tracing past oxygen levels in the oceans. We examine this potential in a marine carbonate section deposited during Cretaceous Ocean Anoxic Event 2 (OAE 2) in the Western Interior Seaway, Colorado. Redox changes are the main source of Cr isotope fractionation in Earth surface environments. Cr(VI), in the form of the chromate oxyanion, is the thermodynamically favoured species in oxygenated seawater. Reduction of Cr(VI) causes light isotopes to partition into Cr(III), which is reactive and susceptible to removal into marine sediment. Therefore, widespread ocean anoxia should correlate with positive shifts in seawater chromate Cr isotope values (δ⁵³Cr), assuming that all Cr input fluxes remained constant during the event. We find instead that inferred seawater δ⁵³Cr values decreased during OAE 2. The minima of the sedimentary δ⁵³Cr excursion coincides with the peak interval of anomalously enriched concentrations of Cr and other trace metals of basaltic affinity attributed to eruption of the Caribbean Large Igneous Province (CLIP). We propose that an anoxic, hydrothermal plume enriched in Cr(III) with low δ⁵³Cr values characteristic of igneous rocks moved from deep waters of the CLIP eruption site in the eastern Pacific into deep waters of the proto-North Atlantic through an oceanic gateway in the Central Americas. Once inside, metal-rich waters upwelled against the surrounding continental margins. CLIP volcanism delivered a submarine weathering flux of Cr to the oceans during OAE 2 that was large enough to mask the expected isotopic response of the ocean Cr cycle to increasing anoxia, particularly in the proto-North Atlantic Ocean.